The electronic structure of single and multiple layers of C(60) molecules deposited on a Rh(100) surface is investigated by means of valence photoemission spectroscopy and density functional theory calculations. The binding of the fullerene monolayer to the metal surface yields the appearance of a new state in the valence band spectrum crossing the Fermi level. Insight into the metallization of the metal/fullerene interface is provided by the calculated electronic structure that allows us to correlate the measured interface state with a strong hybridization between the Rh metal states and the highest and lowest molecular orbitals. This results in a net charge transfer of approximate to 0.5e-0.6e from the metal to the p states of the interfacial C atoms. The charge transfer is shown to be very short range, involving only the C atoms bound to the metal. The electronic structure of the second C(60) layer is already insulating and resembles the one measured for C(60) multilayers supported by the same substrate or calculated for fullerenes isolated in vacuum. The discussion of the results in the context of other C(60)/metal systems highlights the distinctive electronic properties of the molecule/metal interface determined by the Rh support. (c) 2010 American Institute of Physics. [doi: 10.1063/1.3432778]